Chemical additives to make polymeric materials biodegradable

ABSTRACT

The present invention is a new additive material that is physically blended with polymeric material to create at least a partially biodegradable product.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application claims priority to and the benefit of the filing ofU.S. Provisional Application Ser. No. 60/855,430, entitled “ChemicalAdditives to Make Polymeric Materials Biodegradable”, to John A. Lake,et al., filed on Oct. 31, 2006, and the specification thereof isincorporated herein by reference.

BACKGROUND OF THE INVENTION Field of the Invention Technical Field

The present invention relates to new additive materials that arephysically blended with polymeric materials to impart biodegradabilityto resulting articles formed from the polymeric materials.

Plastics are industrially mass-produced and at the same time are usedwidely in daily life and in industrial fields with their usageincreasing greatly. It is desirable to produce plastics that withstandthe forces of nature. Many plastics are not degraded in naturalenvironments, and so in recent years, environmental littering anddestruction due to discarded plastics has occurred. Accordingly, inrecent years, development of plastics that can be biodegraded in naturalenvironments has been desired.

U.S. Pat. No. 7,037,983 issued to Huang, et al, on May 2, 2006 teachesmethods of making functional biodegradable polymers and methods tomodify biodegradable polymers using a direct chemical reaction of abiodegradable polymer in a vinyl monomer. Huang chemically combines theadditive material into the chemical chains of the polymers.

U.S. Patent Application Publication 2004/0076778 teaches a biodegradablebag is taught which comprises a laminated film obtainable by laminatinga sealant layer comprising a biodegradable polymer, a barrier layerhaving an oxygen barrier property and a water vapor barrier property anda barrier layer-supporting substrate layer comprising a biodegradablepolymer, said laminated film being heat-sealed in order for the sealantlayer to be inside. There is no teaching of seeded microbes fordegrading the polymer in the layers.

U.S. Patent Application Publication 2004/0068059 teaches performing acondensation polymerization reaction of a mixture made of the threecomponents: an aliphatic diol, an aliphatic dicarboxylic acid, and analiphatic hydroxycarboxylic acid or its anhydrous cyclic compound (alactone) to synthesize a low molecular weight polyester copolymer havinga weight average molecular weight of 5,000 or more, preferably 10,000 ormore, and adding a bifunctional coupler to the polyester copolymer in amolten state. Further, a high molecular weight aliphatic polyestercopolymer and a high molecular weight aliphatic polyester copolymercontaining polylactic acid having moldable properties is disclosed.These copolymers can be degraded by microorganisms present in soils orwater.

U.S. Patent Application Publication 2003/0157214 teaches a compositionof graft copolymers of polyhydroxy compounds. The composition providesan effective method to create environmentally friendly chewing gum.

Furanone-derived compositions have been known in the art to have variousutilities. For example, U.S. Pat. No. 6,296,889 describes the use ofcertain furanone compounds in conjunction with 1-nonen-3-one to providedairy and coffee aroma flavor enhancement. Specific furanones (forexample,3,-(3,4-difluorophenyl)-4-(4-(methylsulfonyl)phenyl)-2-(5H)-furanone,3-phenyl-4-(4-(methylsulfonyl)phenyl)-2-(5H)-furanone and5,5-dimethyl-4-(4-(methylsulfonyl)phenyl)-3-(3-fluorophenyl)-5H-furan-2-one)have been shown to be cyclooxygenase-2 (COX-2) inhibitors useful intreating certain inflammatory conditions (U.S.

U.S. Pat. No. 5,599,960 issued to Boden et al., on Feb. 4, 1997 teachesa 3,5-dimethyl-pentenyl-dihydro-2(3H)-furanone isomer mixture withorganoleptic properties. The mixture has a sweet, lactonic, coumarinic,jasmine aroma with intense green, citrusy, sweet, lactonic topnotes andbergamot peel and lemony undertones and is a pleasant odor to humans.This aroma is highly desirable in several types of perfume compositions,perfumed articles, colognes, deodorizing compositions and odor maskantcompositions.

BRIEF SUMMARY OF THE INVENTION

One embodiment of the present invention provides a biodegradableadditive for polymeric material comprising a chemo attractant compound;a glutaric acid or its derivative; a carboxylic acid compound with chainlength from 5-18 carbons; a polymer; and a swelling agent. In addition,the additive may further comprise one or more of the following: amicrobe which can digest the polymeric material a compatibilizingadditive, a positive chemotaxis agent to attract the microbes, metal toinduce rusting, colorants, and/or inks, and/or metallic particles toincrease or decrease light reflectance, add strength, slow or preventthe breakdown of a layer or vary the time to break down, or a carrierresin.

In a preferred embodiment, the polymer is selected from the groupconsisting of: polydivinyl benzene, ethylene vinyl acetate copolymers,polyethylene, polypropylene, polystyrene, polyterethalate, polyesters,polyvinyl chloride, polymethyl methacrylate, polycarbonate, polyamide,and any copolymers of said polymers.

In a preferred embodiment the carrier resin is selected from the groupconsisting of: polydivinyl benzene, ethylene vinyl acetate copolymers,maleic anhydride, acrylic acid with polyolefins.

In a more preferred embodiment, the microbe and the furanone aredisposed within a capsule in order to facilitate controlled release ofthe material.

The furanone may be for example 2(3H)-Furanone compound with methane butis not limited thereto.

According to another embodiment a method for creating a layered polymerplastic is disclosed comprising: providing at least one layer of apolymer; and layering products around the polymer to create a newbiodegradable product. In a preferred embodiment, one layer comprises amicrobe suitable for degrading the polymer. In a preferred embodiment,the microbes are applied to the at least one layer using vapordeposition. In a more preferred embodiment the layering is biaxiallyoriented. In another preferred embodiment, the layering is shaped likehoney comb hexagon shapes. In an alternate embodiment, an inner layer isrigid against mechanical stress. In yet another alternative embodiment,at least one layer comprises a fragrance. In a preferred embodiment, atleast one layer is one or more of the following: a smell attractant formicrobes, an initiator that modifies the polymer, has perforations.

In response to the need for a better and more effective way to renderpolymeric materials biodegradable, the present invention teaches how tomake additive materials and how to effectively use those materials torender polymeric materials biodegradable

Therefore it is an object of the present invention to make a widevariety of polymeric materials biodegradable no matter what theirchemical composition.

It is a further object of the present invention to make biologicallysafe and biodegradable polymeric materials without having to chemicallymodify the polymeric molecules.

It is another object of the present invention to have an additivematerial that can make most polymeric compositions biodegradable bymerely mixing it in with the polymeric material any time before thepolymeric material is formed into an article for sale.

One aspect of the present invention provides controlled releasetechnology for the controlled release of perfumes into gaseousenvironments during polymer degradation.

These and other objects of the present invention will become clear tothose of ordinary skill in this art by reviewing this description andclaims appended hereto.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 illustrates one embodiment of making a polymer biodegradable withlayering of additive.

FIG. 2 illustrates size exclusion chromatography of a polymer compositematerial in the presence and absence of additive.

DETAILED DESCRIPTION OF THE INVENTION

As used herein, “a” means one or more.

As used herein, “chemo attractant” is inorganic or organic substancespossessing chemotaxis inducer effect in motile cells.

As used herein “polymer” is a synthetic and/or natural macromoleculescomposed of smaller units called monomers that are bonded together.

Polymers

Polymers are synthetic and natural macromolecules composed of smallerunits called monomers that are bonded together. Thermoplastics are atype of polymer that can melt or deform, melts to a liquid when heatedand freezes to a brittle, glassy state when cooled sufficiently. Mostthermoplastics are high molecular weight polymers whose chains associatethrough weak van der Waals forces (such as polyethylene); strongerdipole-dipole interactions and hydrogen bonding (such as polyamide); orstacking of aromatic rings (such as polystyrene). Thermoplastic polymersdiffer from thermosetting polymers as they can, unlike thermosettingpolymers, be remelted and remoulded. Many thermoplastic materials areaddition polymers; e.g., vinyl chain-growth polymers such aspolyethylene and polypropylene.

The major types of thermoplastics include linear low densitypolyethylene, high density polyethylene, polyvinyl chloride, low densitypolyethylene, polypropylene, polystyrene and other resins. The majorclasses of thermosetting polymer resins include polyester, one of whichis polyethylene terephthalate and polyurethane.

Certain polymers are taught by the literature as not biodegradable oronly very slowly biodegradable. One embodiment of the present inventionenables the acceleration of biodegradation of a wide range of polymersto such an extent as to significantly reduce their environmental impactwithout adversely affecting their desirable physical properties.

These polymers include polystyrene, polyurethane, polyethylene,polypropylene, or polycarbonate plastics. Polymers made from groups suchas aldehydes, methyl, propyl, ethyl, benzyl or hydroxyl groups andpetroleum based polymers are also taught as not biodegradable. Oneembodiment of the present invention is directed to increasing thebiodegradability of non-biodegradable polymers by addition of abiodegradable polymer additive to the polymer composition.

Biodegradable Polymers

Biodegradation is generally considered as comprising enzyme-catalyzedhydrolysis, oxidation, and/or reduction. The enzymes may be eitherendoenzymes which function within the microorganisms or exoenzymes whichfunction outside the microorganisms.

Biodegradation is a functional decay of material, e.g. loss of strength,substance, transparency, or good dielectric properties where it is knownto be identifiable with exposure of the material to a livingenvironment, which may itself be very complex, and the property loss maybe attributable to physical or chemical actions as first steps in anelaborate chain of processes.

A biodegradable polymer is a high molecular weight polymer that, owingto the action of micro- and/or macroorganisms or enzymes, degrades tolower molecular weight compounds. Natural polymers are by definitionthose which are biosynthesized by various routes in the biosphere.Proteins, polysaccharides, nucleic acids, lipids, natural rubber, andlignin, among others, are all biodegradable polymers, but the rate ofthis biodegradation may vary from hours to years depending on the natureof the functional group and degree of complexity. Biopolymers areorganized in different ways at different scales. This hierarchicalarchitecture of natural polymers allows the use of relatively fewstarting molecules (i.e. monomers), which are varied in sequences andconformations at molecular-, nano-, micro-, and macroscale, formingtruly environmentally adaptable polymers.

On the other hand, the repetitive units of synthetic polymers arehydrolyzable, oxidizable, thermally degradable, or degradable by othermeans. Nature also uses these degradation modes, e.g., oxidation orhydrolysis, so in that sense there is no distinction between natural orsynthetic polymers. The catalysts promoting the degradations in nature(catabolisms) are the enzymes, which are grouped in six differentclasses according to the reaction catalyzed. These classes includeoxidoreductase for catalyzing redox reactions, transferase forcatalyzing transfer of functional group reactions, hydrolase forcatalyzing hydrolysis, lyase for catalyzing addition to double bondreactions, isomerase for catalyzing isomerization and ligase forcatalyzing formation of new bonds using ATP.

Biodegradation of oxidizable polymers is generally slower thanbiodegradation of hydrolyzable ones. Even polyethylene, which is ratherinert to direct biodegradation, has been shown to biodegrade afterinitial photo-oxidation. An oxidized polymer is more brittle andhydrophilic than a nonoxidized polymer, which also usually results in amaterial with increased biodegradability. Means to accelerate theoxidation of polymers (for example polyolefins) are presented accordingto one embodiment of the present invention.

For example, by combining a nickel dithiocarbamate (photo antioxidant)with an iron dithiocarbamate (photo proxidant), a wide range ofembrittlement times may be obtained.

One embodiment of the present invention provides for increasedsusceptibility to biodegradation of polymers by means of additivesincluding a biopolymer. In this way a polymer blend is obtained that ismore susceptible to biodegradation.

Combining granular starch mixed with polyethylene together with anunsaturated polymer, a thermal stabilizer, and a transition metalproduce a material with increased susceptibility to photo-oxidation,thermolysis, and biodegradation. This particular material has also aninduction time before degradation may be initiated. The use of starchalone in polyethylene, for example, requires, however, rather largeamounts in order to really create an increase in the biodegradationrate.

According to one embodiment, a filler is added to a composition to beadded to a polymer there by increasing the biodegradability.

Microbial or enzymatic attack of pure aromatic polyester is increased byexposure to certain microbes, for example Trichosporum, athrobacteriaand Asperyillus negs.

Aliphatic polyester degradation is seen as a two-step process: the firstis depolymerization, or surface erosion. The second is enzymatichydrolysis which produces water-insoluble intermediates that can beassimilated by microbial cells.

Polyurethane degradation may occur by fungal degradation, bacterialdegradation and degradation by polyurethane enzymes.

Microbes

A variety of microorganisms, including bacteria and fungi, aid indegrading polymeric materials. Preliminary Review of the Degradation ofCellulosic, Plastic, and Rubber Materials in the Waste Isolation PilotPlant, and Possible Effects of Magnesium Oxide Safety FactorCalculations, Prepared for U.S. EPA Office of Radiation and Indoor Air(Sep. 11, 2006). Actinobacteria are a type of bacteria that are most(ly)commonly found in soil and can thrive in low-nutrient environments. Theycan survive in both aerobic and anaerobic conditions, although most areaerobic. The most important role of the Actinobacteria is decompositionof organic nutrients, such as cellulose, and they are one of the fewbacteria able to consume lignocellulose.

Fungi (molds) commonly require oxygen and a pH range of 4.5 to 5 toproliferate. Fungi grow at temperatures ranging up to 45° C., althoughoptimum growth rates generally occur at temperatures between 30° C. and37° C. Because most fungi require oxygen, they may only be available forcellulosic, plastic and rubber (CPR) degradation before closure and fora relatively short time (compost environment). There is some evidencethat anaerobic fungi may degrade lignocellulosic materials.

Biodegradation processes can affect polymers in a number of ways.Microbial processes that can affect polymers may include mechanicaldamage caused by growing cells, direct enzymatic effects leading tobreakdown of the polymer structure, and secondary biochemical effectscaused by excretion of substances other than enzymes that may directlyaffect the polymer or change environmental conditions, such as pH orredox conditions. Although microorganisms such as bacteria generally arevery specific with respect to the substrate utilized for growth, manyare capable of adapting to other substrates over time. Microorganismsproduce enzymes that catalyze reactions by combining with a specificsubstrate or combination of substrates. The conformation of theseenzymes determines their catalytic reactivity towards polymers.Conformational changes in these enzymes may be induced by the changes inpH, temperature, and other chemical additives.

Microbes and Plastics Degradation

For the enzymatic degradation of synthetic plastic polymers, polymerscontaining hydrolysable groups in the polymer backbone would beespecially prone to microbial attack, because many microorganisms arecapable of producing hydrolases (enzymes catalyzing hydrolysis). Ingeneral, aliphatic polyesters, polyurethane, polyethers, and polyimidesare more easily degraded by commonly occurring microorganisms.Generally, higher molecular weight polymers and branched polymers aremore resistant to microbial degradation. Polyethylene andpolyvinylchloride are considered to be relatively resistant to microbialdegradation. However, some bacterial strains have been identified thatcan degrade polyethylene, including Rhodococcus and B. borstelensis.

The ability of microorganisms to adapt to a new source of nutrients ishighly noteworthy in any evaluation of the microbial degradation ofplastic materials. Evidence of adaptation of bacteria for thedegradation of plastics has been shown in several cases. For example, itwas found that Pseudomonas aeruginosa started proliferation 56 daysafter the bacteria were brought into contact with polyamide-6 polymer.Inoculation of previously untreated polyamide with these bacteriaresulted in immediate growth on the new substrate. Individual species ofbacteria can carry out several different steps of chemical breakdown orbiodegradation. Most toxic compounds are degraded or biodegraded bygroups called consortia. Each species in the group works on a particularstage of the degradation process, and one or more of them together areneeded for the complete degradation or biodegradation or detoxificationprocess. Contaminated vessels containing such things as pesticides,metals, radioactive elements, mixed wastes and the like can be made tocontain microbes that will detoxify and decompose the contaminates andbiodegrade the vessel.

Other microbes that may assist in biodegradation are psychrophiles,mesophiles, thermophiles, actinomycetes, saprophytes, absidia,acremonium, alternaria, amerospore, arthrinium, ascospore, aspergillus,aspergillus caesiellus, aspergillus candidus, aspergillus carneus,aspergillus clavatus, aspergillus deflectus, aspergillus flavus,aspergillus fumigatus, aspergillus glaucus, aspergillus nidulans,aspergillus ochraceus, aspergillus oryzae, aspergillus parasiticus,aspergillus penicilloides, aspergillus restrictus, aspergillus sydowi,aspergillus terreus, aspergillus ustus, aspergillus versicolor,aspergillus/penicillium—like, aureobasidium, basidiomycetes,basidiospore, bipolaris, blastomyces, B. borstelensis, botrytis,candida, cephalosporium, chaetomium, cladosporium, cladosporium fulvum,cladosporium herbarum, cladosporium macrocarpum, cladosporiumsphaerospermum, conidia, conidium, conidobolus, Cryptococcus neoformans,cryptostroma corticale, cunninghamella, curvularia, dreschlera,epicoccum, epidermophyton, fungus, fusarium, fusarium solani,geotrichum, gliocladium, helicomyces, helminthosporium, histoplasma,humicula, hyaline mycelia, memnoniella, microsporum, mold, monilia,mucor, mycelium, myxomycetes, nigrospora, oidium, paecilomyces,papulospora, penicillium, periconia, perithecium, peronospora,phaeohyphomycosis, phoma, pithomyces, rhizomucor, rhizopus, rhodococcus,rhodotorula, rusts, saccharomyces, scopulariopsis, sepedonium, serpulalacrymans, smuts, spegazzinia, spore, sporoschisma, sporothrix,sporotrichum, stachybotrys, stemphylium, syncephalastrum,Thermononespore fusca DSM43793, torula, trichocladium, trichoderma,trichophyton, trichothecium, tritirachium, ulocladium, verticillium,wallemia and yeast.

One or more furanone compounds may be combined to act aschemoattractants for bacteria and or as odorants for the decomposingpolymer. Some furanones, particularly certain halogenated furanones arequorum sensing inhibitors. Quorum sensing inhibitors are typicallylow-molecular-mass molecules that cause significant reduction in quorumsensing microbes. In other words, halogenated furanones kill certainmicrobes. Halogenated furanones prevent bacterial colonization inbacteria such as V. fischeri, Vibrio harveyi, Serratia ficaria and otherbacteria. However, the natural furanones are ineffective against P.aeruginosa, but synthetic furanones can be effective against P.aeruginosa.

Some furanones, including those listed below, are actually chemoattractant agents for bacteria. Suitable furanones may include but arenot limited to: 3,5_dimethylyentenyl_dihydro_(—)2(3H)furanone isomermixtures, emoxyfurane and N-acylhomoserine lactones.

Bacteria that have shown to attract to the furanone compounds listedabove include, but are not limited to C. violaceum,

Other chemo attractant agents include sugars that are not metabolized bythe bacteria. Examples of these chemo attractant agents may include butare not limited to: galactose, galactonate, succinate, malate,aspartate, serine, fumarate, ribose, pyruvate, oxalacetate and otherL-sugar structures and D-sugar structures but not limited thereto.Examples of bacteria attracted to these sugars include, but are notlimited to Escherichia coli, and Salmonella. In a preferred embodimentthe sugar is a non-esterified starch

One embodiment of the present invention is used with any carrier resinsuch as Ethylene-Vinyl Acetate Copolymer with additive ingredients oforganoleptic-Organics i.e. cultured colloids and natural or manmadefibers. When combined in small quantities with any of the plasticresins, the present invention renders the end products biodegradablewhile maintaining their desired characteristics.

An important attribute of the invention is its use without having tosignificantly modify the existing methods of production of plasticproducts. The resulting polymers and plastic products made therefromexhibit the same desired mechanical properties, and have effectivelysimilar shelf-lives as products without the additive, and yet, whendisposed of, are able to at least partially metabolize into inertbiomass by the communities of anaerobic and aerobic microorganismscommonly found almost everywhere on Earth.

This biodegradation process can take place aerobically or anerobically.It can take place with or without the presence of light. Traditionalpolymers are now able to biodegrade in landfill and compost environmentswithin a reasonable amount of time as defined by the EPA to be 30 to 50years on average.

One embodiment of the present invention differs significantly from other“degradable plastics” emerging in the market today because it does notattempt to replace the currently popular plastic resin formulations butinstead enhances them by rendering them biodegradable. One embodiment ofthe present invention is superior to those currently in the market placefor several reasons. Photo-degradable products, for example, do notdegrade in landfills due to the lack of sunlight (they are typicallycovered with another layer of trash before the degradation can occur).At the same time these photo-degradable products present difficultcircumstances for storage before use due to their reactivity to light.Similarly, plastic products manufactured with high amounts of cornstarchand cottonseed fillers fail to breakdown the molecular structure of theproducts' plastic components, partially break down only in commercialcompost facilities, are very expensive to manufacture, and often do notachieve the requisite physical properties.

One embodiment of the present invention allows for a process which firstattracts microorganisms through chemo taxis and then enables themicroorganisms in the environment to metabolize the molecular structureof plastic films. The films may be degraded into an inert humus-likeform that is harmless to the environment. An example of attractingmicroorganisms through chemo taxis is to use a positive chemo taxis,such as a scented polyethylene terephthalate pellet, starch D-sugars notmetabolized by the microbes or furanone that attracts microbes or anycombination thereof.

In a preferred embodiment, several proprietary bio-active compounds arecombined into a master batch pellet that is easily added to plasticresins and colorants. The biodegradation process begins with one or moreproprietary swelling agents that, when combined with heat and moisture,expands the plastics' molecular structure.

After the one or more swelling agents create space within the plastic'smolecular structure, the combination of bio-active compounds discoveredafter significant laboratory trials attracts a colony of microorganismsthat break down the chemical bonds and metabolize the plastic throughnatural microbial processes.

One embodiment of the present invention provides an improved formulationof an additive material that can be added to various polymeric materialsand colorants, and mixed into such materials to make them biodegradablewithout having to chemically alter the polymeric molecules. This isimportant to preserving the formability of the polymeric materials sothat they can be used for their essential purpose of being formed intoarticles that then can be sold into the streams of commerce for use bythe customer. Once the product is used it can be discarded and sent to aland fill where once the products are buried into an environment lackingin oxygen the articles will biodegrade within a reasonably short timethus eliminating a serious environmental problem with the disposal ofplastics in particular.

According to one embodiment of the present invention, an additivecomprises a furanone compound, a glutaric acid, a hexadecanoic acidcompound, a polycaprolactone polymer, a carrier resin to assist withplacing the additive material into the polymeric material in an evenfashion to assure proper biodegradation. The additive may also compriseorganoleptic organic chemicals as swelling agents i.e. natural fibers,cultured colloids, cyclo-dextrin, polylactic acid, etc.

The additive material renders a wide variety of polymeric materialsbiodegradable which would not ordinarily be biodegradable. Examples ofsuch polymeric materials include straight chain and branched chainaddition polymers, copolymers, as well as condensation polymers. Itincludes aliphatic as well as aromatic based polymer materials. Morespecifically the additive is effective in rendering polyethylenes,polypropylenes, polyvinyl acetates, poly lactic acids, polycaprolactones, poly glycolic acids, poly lactic_co_glycolic acids,polyvinyl chlorides, polystyrenes, polyterethalates, and polyesters,polyamides biodegradable so that they may be simply added to a land filland in the presence or absence of oxygen to initiate biodegradation.

According to one embodiment of the present invention, an additivecomprises a mixture of a furanone compound, a glutaric acid, ahexadecanoic acid compound, a polycaprolactone polymer, organolepticswelling agent (natural fiber, cultured colloid, cyclo-dextri,Polylactic acid, etc.) and a carrier resin to assist with placing theadditive material into the polymeric material to be renderedbiodegradable in an even fashion to assure proper biodegradation.Preferably, the furanone compound is in a range equal to or greater than0-20% by weight. In a more preferred embodiment, the furanone compoundis 20-40% by weight, more preferably 40-60% by weight, still morepreferably 60-80% by weight or preferably 80-100% by weight of the totaladditive. The glutaric acid is in the range equal to or greater than0-20% by weight of the total additive. In a more preferred embodiment,the glutaric acid is 20-40% by weight, more preferably 40-60% by weight,still more preferably 60-80% by weight or preferably 80-100% by weight,20-40%, 40-60%, 60-80% or 80-100% by weight of the total additive. Thehexadecanoic acid compound is in the range equal to or greater than0-20% by weight of the total additive. In a more preferred embodiment,the hexadecanoic acid is 20-40% by weight, more preferably 40-60% byweight, still more preferably 60-80% by weight or preferably 80-100% byweight, 20-40%, 40-60%, 60-80% or 80-100% by weight of the totaladditive. The polycaprolactone polymer is in the range equal to orgreater than 0-20% by weight of the total additive. In a more preferredembodiment, the polycaprolactone is 20-40% by weight, more preferably40-60% by weight, still more preferably 60-80% by weight or preferably80-100% by weight, 20-40%, 40-60%, 60-80% or 80-100% by weight of thetotal additive. The natural or manmade organoleptic swelling agent (e.g.natural fiber, cultured colloid, cyclo-dextrin, or polylactic acid) isin the range equal to or greater than 0-20% by weight of the additive.In a more preferred embodiment, the organoleptic swelling agent is20-40% by weight, more swelling agent is 20-40% by weight, morepreferably 40-60% by weight, still more preferably 60-80% by weight orpreferably 80-100% by weight, 20-40%, 40-60%, 60-80% or 80-100% byweight of the total additive. Scanning Electron Microscope (SEM) photoswith scientific analysis have provided proof of biodegradation takingplace using the above mixture of chemical compounds in three monthstime. See examples below for further discussion regarding the SEMphotos.

The glutaric acid compound may be propylglutaric acid for example, butis not limited thereto.

The polycaprolactone polymer may be selected from, but is not limited tothe group of: polycaprolactone, poly (lactic acid), poly (glycolicacid), poly (lactic_co_glycolic acid).

The swelling agents may be selected from, but is not limited to thegroup of: natural fibers, cultured colloids, organoleptic compounds,cyclo-dextrin.

The carrier resin may be selected from, but is not limited to the groupof: ethylene vinyl acetate, poly vinyl acetate, maleic anhydride, andacrylic acid with polyolefins.

Once the additive has been formulated, it must be rendered into a formthat will allow even distribution of the additive into the polymericmaterial that is desired to be made biodegradable. This can beaccomplished by granulation, powdering, making an emulsion, suspension,or other medium of similar even consistency.

In a preferred embodiment, the additive is blended into the polymericmaterial just before sending the polymeric material to the formingmachinery for making the desired article or finished polymeric product.

Any carrier resin may be used with one embodiment of the presentinvention (such as poly-vinyl acetate, ethyl vinyl acetate, etc.) wherepoly olefins or any plastic material that these carrier resins arecompatible with can be combined chemically and allow for the dispersionof the additive.

Current additives without the carrier resins may be used in varyingproportions and blended in with any plastic product, biodegradableadditive or product such as poly lactic acid, oxy degradable additives,or non plastic product.

Further, the additive of the present invention will work with renewableresources (Green) plastic products such as Duponts Sorano. The currentinvention will also work with any form of plastic molding process thathas been created for the purpose of producing end products, i.e.injection, thermoforming, blown, extrusion, roto, spray-on coating ordipping on layer into another.

In yet another preferred embodiment, the invention is a film with one ormore layers, where each layer includes a different product orcombination of products to allow for new biodegradable products to bemanufactured that have improved properties. These properties wouldinclude: all the benefits of a poly lactic acid product (meets the ASTMD-6400-99 standard for biodegradability in 90 days) and those of apolyethylene plastic layer that retains its shelf life indefinitely andprovides for strength, protection from light, oxygen, moisture, heat,and mechanical stress. Microbes can be applied to the layers using vapordeposition, wherein other materials are in the other layers and morethan one species of microbes can be selectively applied to the layers.For instance, each microbe can be selected for its capability to produceone or more beneficial by-products, such as methane, ozone, or oxygen.

In addition, any of the layers could have micro perforations orperforations of varying sizes and shapes that would allow for varyingamounts for moisture, water, liquids, gas, etc. to pass through a lesspermeable, biodegradable plastic layer made using the biodegradableadditive technology. Once the gas, liquid or moisture substance passesthrough an outer layer (which is of varying dimensions, sizes and shapesas well as physical and chemical properties), the inner layers willbegin to biodegrade at a pre-designed rate. For example, a bottle thathas a thin layer of polyethylene plastic with the biodegradable additiveon the exterior can sustain a full shelf life because the interior layercontacting a liquid is keeping the liquid away from the biodegradablematerial on the outside of the bottle. Also, the inner material providesrigidity against mechanical stress. Once the bottle is put intolandfill, moisture and microbes will attack the outer portion of thebottle and degrade it quickly. Finally, the inner layer of film willcome into contact with microbes and biodegrade at a different rate oftime.

Another embodiment is a multilayered biaxial oriented film (made frompolypropylene, polyethylene, polystyrene, etc.) that has layer(s) ofstarch based materials or green recycled polyethylene terephthalatematerials or a combination of material(s) in combination with the normalplastic materials with the new biodegradable additive such as plasticwith additive according to one embodiment of the present inventioncovering composite polymer material.

Any variation of the layering approach and/or using some other designlike honey comb hexagon shapes or any other can be employed using thepresent invention.

In a further preferred embodiment, metals are part of the additive'scomposition to induce rusting with or without the layered approach.Metals add strength to a given item while allowing them to rust throughand allow for degrading. All types of metal particles can be included inthe mix to produce new variations with differing properties. Since rustparticles are air borne the new material would begin to rust and degradeonce it comes into contact with moisture.

Colorants, inks and metallic particles are preferably added to theadditive or into any layer in any combination of the additive. Thecolorants, inks and metallic product increase or decrease light (UV)reflectance, add strength, slow or prevent the breakdown of a layer, orvary the time to break down i.e. degradation or biodegradation at aspecific time.

In another preferred embodiment, the introduction of a marker for thepurpose of quality control (important to know that a designed % by loadweight of the invention additive is present) is a part of the additive.Materials such as: CS131, C-14, phosphorescent materials, minerals thatglow in the dark, alpha emitting particles with short half life that theconcentrations can be easily measured with instrumentation in use todayand are easily used to ensure the quality and effectiveness of theadditive.

The present invention biodegrades high impact polystyrene, polystyrene,polypropylene, polyethylene terephthalate, high density polyethylene,low density polyethylene, and others. Scanning Electron Microscope wasused to test the biodegradability of these materials when mixed in a 1%to 5% by load weight of additive to plastic.

The following is an example of a layer composition of a preferredembodiment. Multilayered films, such as ultra multilayered polyethyleneterephthalate (trade marked Tetoron MLF), which is extremely thin filmtechnology that laminates 200 to 300 layers or more of two types ofpolymer films has been improved on but not limited to the followingexample:

-   -   Layer 1 (UV or light prevention layer), Layer 2 (Layer of        biodegrading microbes suspended in plastic), Layer 3 (Fragrance        or flavoring layer), Layer 4 (Smell attractant layer for        microbes), Layer 5 (Green product layer like such as Dupont        Sarano™), Layer 6 (Initiators layer that modify the polymers        i.e. light, heat, high energy, free radicals), Layer 7        (Remembrance polymer layer that returns a molecules to previous        shapes when a pre designed temperature or condition is met),        Layer 8 (Perforated or micro perforated layer(s) with the        additive that allow moisture/water or some specified inducer in        the form of a gas or liquid through the perforations and into        the inner layer allowing for the stimulation of the        microorganisms (bacteria, mold fungi, yeast, enzymes, etc) and        the biodegradation process to begin.

Referring now to FIG. 1, one embodiment of creating a biodegradablepolymer is illustrated. Layers can be rearranged into most anycombination and additional layers can be added or eliminated asrequired. The microbe layer(s) (Layer 2 of the example) comprises:carbon dioxide eating microbes and Pseudomonas putida, which occursnaturally in soil and can live on styrene. The microbes may be suspendedand resuspended upon interaction with water or other fluid. The microbesmay be oil eating microbes such as alcanivorax borkumensis.

An example of suitable microbes mixed into the additive of the presentinvention is called chemo heterotrophic prokaryotes. These bacteriafunction as decomposers breaking down corpses, dead vegetation, andwaste products Nitrogen-fixing prokaryotes. Many prokaryotes live withother organisms in symbiotic relationships such as mutualism andcommensalisms. To allow for a particular form on microbe (mold, fungi,bacteria, etc.) to function in decomposing/biodegrading of plastic, theproper nutrients is important in the plastic for them to feed on it (inthe case of nitrogen fixing bacteria it would be a nitrogen, sulfurfixing bacteria sulfur, etc.). The microbes may be able to remaindormant while suspended in a thin layer matrix of some plastic or othercompound. The microbes are activated in use when they come into contactwith an initiator such as water and begin to decompose or biodegrade theplastic containing the specific nutrient e.g. nitrogen that they musthave in order to thrive. Once the nutrient is gone, the microbes die andreturn to the soil.

In one preferred embodiment, the microbe and furanone material aredispersed within a capsule in order to facilitate controlled release ofthe additive. The capsule acts to contain the microbes and furanone andseparate it from the polymers so that it doesn't get mixed directly intothe polymers during the melting phase.

In another preferred embodiment, the additive includes one or moreantioxidants that are used to control the biodegradation rate.Antioxidants can be enzymatically coupled to biodegradable monomers suchthat the resulting biodegradable polymer retains antioxidant function.Antioxidant-couple biodegradable polymers can be produced to result inthe antioxidant coupled polymer degrading at a rate consistent with aneffective administration rate of the antioxidant. Antioxidants arechosen based upon the specific application, and the biodegradablemonomers may be either synthetic or natural.

In yet another preferred embodiment, the additive is dispersed intopolymeric compositions using one or more supercritical fluids. Thesupercritical fluids are used to diffuse additives into raw materialpolymeric resin or even finished polymeric products. This supercriticalinterdiffusion process can be applied repeatedly without ruining ordamaging the polymer system. This establishes total reversibility of theprocess. The process for treating polymeric resins with supercriticalfluids includes: (1) supercritical diffusion of one or more additivesinto a polymeric resin; (2) concurrent compounding in the supercriticalsupercritical fluid; and (3) further process of the resulting infused orinterdiffused polymeric resin by known techniques to yield the desiredfinal product(s).

In a further preferred embodiment, the microbes are geneticallyengineered and customized for the particular biodegradable polymericmaterial. Genetically engineered microbes with protease specific for abiodegradable plastic (for example, poly caprolactone). Thesegenetically engineered microbes are designed to excrete beneficial gasesand energy biproducts. These microbes use enzyme-based routes tomonomer, oligomer and polymer synthesis as well as polymer modification.

EXAMPLE 1

An Example composition of a preferred embodiment is shown below foraddition to a high density polyethylene. In order to make the highdensity polyethylene biodegradable, blend together the additivecomponents in the following proportions:

The furanone compound in a range equal to or greater than about 0-20%,or about 20-40%, or about 40-60%, or about 60-80% or about 80-100% byload weight of the total additive; the glutaric acid in the range equalto or greater than about 0-20%, or about 20-40%, about 40-60%, about60-80% or about 80-100% by weight of the total additive; thehexadecanoic acid compound in the range equal to or greater than about0-20%, or about 20-40%, or about 40-60%, or about 60-80% or about80-100% by weight of the total additive; the polycaprolactone polymer inthe range equal to or greater than about 0-20%, or about 20-40%, orabout 40-60%, or about 60-80% or about 80-100% by weight of the totaladditive; the polycaprolactone, poly(lactic acid), poly(glycolic acid)and poly(lactic_co_glycolic acid) in the range equal to or greater thanabout 0-20%, or about 20-40%, or about 40-60%, or about 60-80% or about80-100% by weight of the total additive and natural or manmadeorganoleptic swelling agent (natural fiber, cultured colloid,cyclo-dextrin, Polylactic acid, etc.) in the range equal to or greaterthan about 0-20%, or about 20-40%, or about 40-60%, or about 60-80% orabout 80-100% by weight of the total additive.

Testing results from several independent testing laboratories haveestablished the biodegradability of plastic test films, foams and otherforms which utilized the biodegradable formulation. The tests concludedthat the films, foams and other forms were biodegradable under short andlong-term anaerobic and aerobic conditions.

EXAMPLE 2

Samples of polyvinylchloride foam with additive (sample A) and withoutadditive (sample B) were examined under a Scanning Electron Microscope(SEM). In addition, samples of polyvinylchloride foam with additive(sample C) and without additive (sample D) were sonicated in detergentfor 5 minutes to remove attached biofilm and microbial colonies.Subsamples of approximately 1 square centimeter were cut from largersamples to prepare for imaging.

Analysis of the samples was carried out on a JEOL 5800LV SEM. The SEMwas equipped with an Oxford Instruments Energy Dispersive X-rayspectrometer (EDX) and an Oxford X-ray analyzer and image system.Accelerating voltage was 15 kV with a beam current of approximately 0.01nA.

It was observed that the sample A surface displayed a large amount ofbiofilm attached. The biofilm occupied depressions in the surface. Inother areas, the biofilm and colonies sit in large continuousdepressions. Also visible were cracks in the polyvinylchloride whichwere exposed by shrinkage of the biofilm during drying.

It was observed that the sample C surface displayed shallow depressionsunder the microbial colonies after they had been removed. Thesedepressions were irregular in outline, reflecting the irregular outlineof the microbial colonies.

It was observed that the sample B surface displayed a large amount ofbiofilm attached. It was observed that the sample D surface displayed nobiofilm or colonies. Only a few depressions were observed that could beidentified as associated with microbial colonies. The depressions seenon the surface of sample D were much less common than on sample C.

Based on the example above, it is apparent that the microbial coloniesare embedded in the surface of the treated sample, mostly occurring inshallow depressions. The microbes tenaciously attached to the treatedsurface and there were more colonies present, as compared to theuntreated sample. The depressions under the colonies indicate that theyare degrading the material much faster than the untreatedpolyvinylchloride, due to the additive present in the treated sample.The additive is not present in the control sample, and microbialdegradation is much slower there.

EXAMPLE 3

Samples of polyethylenepthalate with additive (sample A) and withoutadditive (sample B) were examined under a SEM. Both samples were cleanedin an ultrasonic cleaner with a mild detergent.

Analysis of the samples was carried out in the same way that the samplesin Example 2, were carried out with the same instrument.

It was observed that sample A surface displayed bubbles just below thesurface, broken bubbles at the surface, sub-parallel striations andscratches and other mechanical damage. Sample A shows significantevidence of biodegradation.

It was observed that sample B surface displayed a very smooth surfacewhere most defects were a result of mechanical processes.

Sample A shows significant differences from sample B. For example,sample A shows numerous bubbles, possibly from microbial gas productionwithin the plastic, and odd ribbon-like defects of unknown origin, inaddition to sloughing skin. Sample B shows little effect. Sample A isbeing severely degraded, while sample B is only slightly degraded.

EXAMPLE 4

Samples of expanded polystyrene foam with additive (sample A) andwithout additive (sample B) were examined under a SEM.

Analysis of the samples was carried out in the same way that the samplesin Example 2, were carried out with the same instrument.

It was observed that sample A surface displayed several types of surfacedamage, such as a large ragged holes, and ragged edges and cracks aroundthe holes.

It was observed that sample B surface displayed smooth holes most likelyrelated to the foam making process.

Surface degradation is present in sample A and it is believed that thejagged holes in sample A are of a different origin than the smooth holeson sample B. Sample A exhibits significant differences from sample B.Thus, the changes to sample A are a result from the additive.

EXAMPLE 5

Samples of high impact polystyrene nursery plant labels with additive(sample A) and without additive (sample B) were examined under a SEM.

Analysis of the samples was carried out in the same way that the samplesin Example 2, were carried out with the same instrument.

It was observed that sample A surface numerous had irregular pits andsmaller crater-like holes. A surface layer cracking and peeling awayproduced the large pits. The smaller crater-like holes could be seenwithin the shallow pits. The small holes had no apparent relationship tothe tensional cracks seen around the large pits.

It was observed that sample B surface displayed an inherent surfaceroughness, but showed little in the way of degradation. A few surfacedefects were observed, but they were most likely due to mechanicaldamage rather than degradation.

Sample A and sample B displayed obvious differences. Sample A showed alarge number of pits and cracks that did not appear on sample B. Thesurface of sample A was highly altered. Since major changes onlyoccurred on sample A, they were most likely a result of the additiveused to treat sample A.

EXAMPLE 6

Samples of bubble wrap with additive (sample A) and without additive(sample B) were examined under a SEM. In addition, samples of polyvinylchloride foam with additive (sample C) and without additive (sample D)were sonicated in detergent for 5 minutes to remove attached biofilm andmicrobial colonies.

Analysis of the samples was carried out in the same way that the samplesin Example 2, were carried out with the same instrument.

It was observed that sample A surface showed a diverse and thrivingmicrobial community attached to the bubble wrap. There were also curvedpits in the bubble wrap due to dissolution of the plastic by attachedbacteria.

It was observed that sample C surface displayed abundant small circularpits. These pits may be due to direct dissolution by microbes attachedto the surface.

It was observed that sample B surface was smooth even with a largequantity of microbes attached. The community appeared to be a differencecommunity than observed on sample A.

It was observed that sample D surface was smooth and fairly featureless,but exhibited a pattern of raised ridges that are roughly parallel.There were some pits, but they were much smaller than the bacteriaindicating that the pits were probably not produced by the bacteria.

Samples A and C displayed obvious differences than samples B and D. Pitsand surface defects were widespread on samples A and C, but were presentto a much lesser extent on samples B and D. Pits of all sizes and othersurface features were exceedingly abundant across samples A and C, whileless common on samples B and D. The pits on samples A and C were mostlikely related to microbial breakdown of the plastic, since they wereoften the same size as the bacteria.

EXAMPLE 7

Samples of shoe, shoe sole and shoe Mogo plaque made from polyethylenepolymeric material with 1% per weight load additive (sample A), shoesole and shoe Mogo plaque with 5% per weight load additive (sample B)and shoe, shoe sole and shoe Mogo plaque without additive (sample C)were placed in an anaerobic digester environment analogous to alandfill. The samples were placed within containers that were positionedunderneath a large diameter effluent discharge pipe flowing at a fairlyconstant rate and temperature. The samples were completely covered inliquid waste. The samples were covered in liquid waste for 253 days.

At the end of 4 months, 6 months and 8 months, samples A, B and C werecollected, cleaned with warm water and soap in an ultrasonic cleaner andsubmitted for examination of the plastic biodegradation.

Attenuated Total Reflectance Analysis

An attenuated total reflectance (ATR) analysis was performed on all ofthe samples in Example 7. The ATR spectra were recorded for thesesamples using Perkin-Elmer 16PC spectrometer. All the samples werescanned in the range of 4000 to 800 cm⁻¹. The spectra indicate slightchange in samples A and B compared to sample C. In comparing the ATRspectrum from the 4 month mark to the 8 month mark, sample A showed asignificant increase in biodegradation. Biodegradation for sample Aincrease from 2.7% to 15.8%.

The ATR spectrum from the 4 month mark for sample B showed a degradationrate of 7.65%.

Differential Scanning Calorimetry (DSC) Studies

The mechanical and thermal properties of the samples in Example 7significantly depend on the crystal structure, degree of crystallinity,molecular weight and branching. The temperatures of the melting rangeand glass transition point vary strongly with the polymer type.

For the samples, the interest was mainly focused on the glass transitiontemperature (Tg), melting range and heat of fusion (crystallinity), anddecomposition of the material.

The DSC results show that for sample B, the exothermic (crystallization)peak shifted to a different temperature compared to sample C. This shiftis due in part to biodegradation.

Based on the analytical data above, samples A and B are undergoingbiodegradation.

Referring now to FIG. 2, a size exclusion chromatographic (SEC) analysesof polyethylene samples with and without additive were carried out using98% tetrahydrofuran (THF) and 2% triethyl amine as the mobile phase. Thesamples submitted were: 1) Shoe (control—does not contain additive), 2)Shoe sole (control), 3) Shoe Mogo plaque (control), 4) Shoe(treated—contains 5% Bio-Batch per weight load), 5) Shoe sole(treated—contains 1% Bio-Batch per weight load), 6) Shoe sole(treated—contains 5% Bio-Batch per weight load), 7) Shoe Mogo plaque(treated—contains 1% Bio-Batch per weight load), 8) Shoe Mogo plaque(treated—contains 5% Bio-Batch per weight load).

The samples were dissolved in mobile phase and filtered before analysis.Based on the chromatograms presented above the peak in the controlsample at retention time 4.5 minutes has disappeared in the 5% biobatchsample and has decreased in 1% biobatch sample. The disappearance ofthis high molecular weight peak is an indication of materialdegradation. Also another indication is the increase in the peak areafor low molecular weight fraction at retention time 9.4 minutes. Takentogether, it appears that the samples tested above have undergonebiodegradation of about 4%.

However, to the touch, the treated samples at the end of an 8 month testare distinctly different than the control samples. They are moremalleable and flexible than the controls. This is due to thedeterioration of the chemical composition in the treated samples versusthe control samples.

Based on the FTIR/ATR, DSC and SEC analyses it is clear that the samplesshow evidence of about 4% biodegradation.

EXAMPLE 8

Further ATR analysis of polystyrene treated with additive (Sample A) andpolystyrene that is untreated (sample B) was conducted. The ATR spectrafor sample B1 indicates peaks at 2913.33, 2850.43, 2360 and 2333.33,1236.66 and 1016.66. The treated sample shows peaks at 2915.21, 2847.22,2362.31, 2336.88, 1736.55, 1460.41, 1238.22, and 1017.78. Since the mainabsorptions of the treated polystyrene are approximately 2935-2860 cm-1and there are also absorptions at 1460 and 724 cm 1 the compound is along linear aliphatic chain. The peak at 1736 is probably an amide orcarboxylate (carboxylic acid salt or ketone which is an indication ofthe presence of carbonyl (C═O) group. The treated sample demonstratessigns of microbial degradation.

EXAMPLE 8

Polypropylene samples of 1 cm were examined by SEM for evidence ofbiodegradation is sample A treated with additive and sample B untreatedwith additive. SEM analysis was conducted as described in Example 1.

Sample A demonstrated abundant pits created by the microbial coloniesand biofilm. The holes and pits range in size from about 1-2 um to about10-50 um and larger. The holes contain visible microbes. In addition thesurface shows sloughing and lifting which is attributable in part to themicrobial action in the subsurface.

In contrast sample B demonstrates a smooth surface without pits andholes of the type observed in sample A. Untreated Sample B does notdemonstrate outer skin that has developed on the treated sample.

Although the invention has been described in detail with particularreference to these preferred embodiments, other embodiments can achievethe same results. Variations and modifications of the present inventionwill be obvious to those skilled in the art and it is intended to coverin the appended claims all such modifications and equivalents. Theentire disclosure of all references, applications, patents, andpublications cited above are hereby incorporated by reference.

1. A method of creating a layered polymeric plastic or compositecomprising: providing one or more layers of a polymer that is notbiodegradable; and layering the polymer with a composition comprising achemo attractant compound, a glutaric acid, and a carboxylic acidcompound on, between or around the polymer layers to create a newbiodegradable product wherein the polymer is at least partiallybiodegradable.
 2. The method of claim 1 wherein at least one layercomprises an enzyme produced by microorganisms suitable for degradingthe polymer.
 3. The method of claim 2 wherein the enzymes are applied toat least one layer using vapor deposition.
 4. The method of claim 1wherein at least one layer has perforations.
 5. The method of claim 1wherein at least one layer is biaxially oriented.
 6. The method of claim1 wherein at least one layer is shaped like honeycomb hexagon shapes. 7.The method of claim 1 wherein at least one layer is rigid againstmechanical stress.
 8. The method of claim 1 wherein at least one layercomprises a fragrance.
 9. The method of claim 1 wherein at least onelayer comprises a smell attractant for microorganisms.
 10. The method ofclaim 1 wherein at least one layer comprises an initiator that modifiesthe polymer.
 11. The method of claim 1 wherein at least one layer ofsaid composite comprises a paper composition.
 12. The method of claim 1wherein at least one layer of said composite comprises a metalliccomposition.